Complex amine products with dialkyl zinc dithiocarbamates as pesticides



.nature are preferred, particularly amines and diamines, such as butylamine, hex- .ade'cyl amine, dimethyl amine, diamylwamine, ethylenediamine, hexadecyl propylene diamine,

dlbutyl ethylene diamine, cyclohexylamine, piparison with.otherpesticides are given in detail.

Patented Mar. 11, 1952 COMPLEX AMINE PRODUCTS WITH DI- ALKYLZINODITHIOCARBAMATES AS PESTICIDES William D. Stewart and John H.Standen, Yon kers, N. Y., assignors to The B. F. Goodrich Company, NewYork, N. Y.-, a corporation of New York N Drawing. Application April 2,1945, Serial No. 586,281

14 Claims.

This invention relates to pest control compositions and moreparticularly to compositions which are useful as bactericides,fungicides and insecticides.

This invention has for its general object the provision of new anduseful compositions having the power of killing or repellingeconomically or physiologically harmful pests, such as bacteria,

' compositions which either kill or repel such pests.

Other objects will appear hereinafter.

These objects are accomplished by the following invention of pesticidalcompositions comprising as an essential active ingredient a reactionproduct of a zinc dithiocarbamate, and an amine having at least oneactive hydrogen in the amino group and especially .amines of analiphatic nature.

The zinc dithiocarbamates with which amines I may be reacted to give thecompounds which are useful according to this invention are those inwhich the dithiocarbamate radical contains a secondary or tertiarynitrogen group, the same resulting from the interaction of a primary orsecondary amine and carbon bisulfide, in accordance with the equation:

. a metallicradical or the equivalent being present during the reactionto yield the acid in the form of its salt. R1 and R2 mayrepresent oneorganic group and hydrogen or two individual organic groups, such as twomethyl groups, or to ether they may represent one bivalent group such asa pentamethylene group present in piperidene or an oxy diethylene grouppresent in morpholine. Preferably, R1 and R2 will be aliphatic in natureincluding such representative groups as alkyl, alicyclic, aralkyl andthe like.

The amine which is added to or combined with a zincdithiocarbamate maybe any of the organic amines available having at least one hydrogen atomin theamino group, but amines of aliphatic the alkyl peridene,symmetrical dimethyl ethylene diamine, symmetrical diethyl triethylenediamine, and especially those having a cyclohexyl group and an alkylgroup of no'more than'eight carbon atoms such as N-butylcyclohexylamine, N-ethyl cyclohexylamine, N-methyl cyclohexylamine, andthe like. The term "amine as employed in the specification and claimsisintended to include all the amines of the type indicated of which thepreceding are merely examples.

The addition products which are preferred as pesticides are thoseproducts formed by the reaction of equimolecular portions of a zincdithiocarbamate and an amine. Said addition products are prepared bybringingtogether the zinc dithiocarbamate and the amine, preferably inthe presence of a reaction diluent such as water, alcohol, gasoline, andthe like. i To speed up the reaction, the mixture may be heated, the

' boiling point of the common volatile solvents being a convenienttemperature. The procedure for these reactions. is more fully describedin the patents and in the literature which are concerned with themethods of preparing these addition products. One of the physicalproperties of these products which aids in their applicationaspesticides is their solubility in solvents or mixtures of solvents.

We have discovered that these addition products are highly efilcientfungicides and insecticides, being effective in aqueousdispers'ioii asdilute as 0.1 to 10 p. p. in. against Cutest-quinspecific zincdithiocarbamate and amine addition products to bactericidal. fungicidaland-ins'ecticidal usesr These examples are intended to be illustrativeandnotlimiting. In each test various amounts of the specific additionproduct were employed, but only'those tests which illustrate the.remarkable effectiveness of the mate- .r-ials or .the results which canbe used for com- Example I Bean foliage is dipped in an 05% aqueousdispersion of the 1:1 addition product of cyclohexylamine and zincdimethyl dithiocarbamate and then placed in Petri dishes. Mexican beanbeetles and Japanese beetles are then placed on the treated foliagewhile wet in the Petri dishes, and the dishes are covered. By thistreatment all the beetles are dead within 24 hours with no damage to thefoliage.

Example 11 Ten Calex qaznquefasciatas larvae five to six days old areplaced in aqueous dispersions containing respectively 1 p. p. m. and p.p. m. .of the 1:1 addition product of cyclohexylamine and zinc dimethyldithiocarbamate in duplicate sets which are then incubated for 16 hoursat 29 C. The dispersion containing 1 p. p. m. of the addition productkilled 80% of the larvae; the dispersion containing 10 p. p. m. of theaddition product killed 100% of the larvae.

Example III Bean foliage is dipped in a 0.5% aqueous dispersion of the1:1 addition product of the ethylene diamine and zinc dimethyldithiocarbamate and then placed in Petri dishes. A known number ofJapanese beetles are placed on the wet treated bean foliage in the Petridishes and the dishes are covered. By this treatment all of the beetlesare dead within 24 hours with no damage to the foliage. When Japanesebeetles were immersed in the above 0.5% aqueous dispersion and placed onbean foliage in Petri dishes, there was no feeding and all of thebeetles were dead within 24 hours.

From these examples it is evident that these addition products can besuccessfully used as insecticides. They can also be used as a spray bydissolving them in a solvent which can be used as an insecticidecarrier. Other insecticide materials such as rotenone may beincorporated to produce a spray of general utility. Where a dusttypeinsecticide is desired, these addition products can be milled with talcor bentonite in the proper proportions to produce a dust which will beeffective. These materials can also be prepared as aerosols and be usedwith satisfactory results.

The reaction products of amines and zinc dit iocarbamates are notlimited in use to insecticides but also are very effective asfungicides. The following examples illustrate their ability to preventthe growth of fungi and molds.

Example IV In an agar plate test to determine fungicidal activity, the1:1 addition product of cyclohexylamine and zinc dimethyldithiocarbamate is incorporated into Difco malt extract a ar, thetreated agar is then poured into Petri dishes, and the agar nutrient isinoculated by spraying same with a spore suspension of Alternaria 307mmand others with a spore suspension of Sclerotinia fructicola by means ofan atomizer. Bv this treatment it was found that when 1 part per millionof the chemical was present none of the spores of either fun usgerminated when incubated for 3 days at 21 C.

Example V 4 dimethyl dithiocarbamate is added in the proportion of 1 p.p. m. to spore suspensions of Alternaria solam' and Sclerotim'afructicola each in a 1% orange juice solution containing 50,000 5spores/ml. Small droplets of these mixtures are placed on microscopicslides and incubated at 21 C. in a moist chamber for 18 to 24 hours. Onexamination it is found that none of the spores germinated in the sporesuspensions thus treated. These addition products are also effective asfungicides for the treatment of cotton fabrics to prevent destruction ofthe fabric by "mildew which is the destruction of the cotton fibers bymold (fungi) and bacteria. The molds, microorganisms belonging to thefamily of plants known as thallophytic plants, are plants which derivetheir nourishment wholly, or almost wholly, from organic compounds. Themolds responsible for rotting are capable of converting the 0 carbon ofthe cotton cellulose into a readily assimilable food which can result incomplete destruction of the cotton material. This destruc- 'tion isexceedingly rapid under tropical conditions, for, if the fabric orcotton material is in 25 contact with the ground, there is completedestruction of the material in 5 to 7 davs. The following exampledemonstrates the ability of these addition compounds to prevent mildew"destruction to cotton fabric.

Example VI Test pieces of cotton fabrics are dipped in a 1% aqueousdispersionof the 1:1 addition product of cyclohexylamine and zincdimethyl dithiocarbamate and then buried with untreated test pieces insoil heavily infested with cellulose-decomposing microorganisms. After21 days there is very little change in appearance or strength of thetreated fabric, while the untreated test piece is virtually destroyed bymildew.

The 1:1 addition product of ethylene diamine and zinc dimethyldithiocarbamate is equally effective against fungi. The followingexample illustrates its effectiveness in the spore suspension test.

Example VII A concentration of 1 p. p. m. of the 1:1 addition product ofethylene diamine and zinc dimethyl dithiocarbamate is added to sporesuspensions of Alternaria solam' and Sclerotinz'a fructicola in orangejuice solutions and tested as in Example V. After incubation in a moistchamber for 18 to 24 hours at 21 0., none of the spores had germinated.

These addition products are also effective bactei'lcides. Their abilityto kill bacteria is illustrated in the following example.

Example VIII The 1:1 addition product of cyclohexylamine and zincdimethyl dithiocarbamate was used as a bactericide over a wide range ofconcentrations to determine its killing power on Staphylococcas aureas,but only the lo er port on of the killing concentrations are given. 10to 1.00

p. p. m. of the 1:1 addition product of cyclohexylamine and zincdimethyl dithiocarbamate are incorporated into 10 ml. portions of Difco7 nutrient broth and 10% beef serum containing Staphylococcus aureus.After incubation at 40 C. for 24 hours, it is found that 10 p. p. m. is

sufficient to kill the bacteria in the broth, while 100 p. p. m. willkill the bacteria in the serum.'

The addition products of amines with zinc dithiocarbamates are not onlyuseful in killing Mexican bean beetles, Japanese beetles and mosquitolarvae, but they also may" be usedto kill or repel other insect pestssuch as codling moths, carpet beetles, confused flour beetle adults andlarvae, flies, moths, ticks, fleas, and the like.

These addition products may be used. in combination with other activeingredients such as metallic arsenicals, fluosilicates, organicthiocyanates, phenothiazina. nicotine, pyrethruin,

isobutylundecylenam-ide, and others. These mixtures may alsobe dilutedwith inert ingredients such as talc, calcium carbonate and tricalciumphosphate, or they may be dissolved or suspended in petroleumhydrocarbons, water, or alcohol. Dispersing, wetting and spreadingagents such as lauryl alcohol, long-chain alcohol sulfates, sulfated andsulfonated alcohols, sodium salts of sulfated alcohols, sulfonatedaliphatic derivatives, sulfonated aromatic and alkylaryl derivatives,hexahydric alcohol, esters of fatty acids, pine oils, and soybeanlecithin may be used to aid in stabilizing the suspensions. Adhesives orsticking agents such as milk products, flour, gelatine and fish oils maybe incorporated into the mixture to increase the retention or tenacityof spray deposits.

By employing these addition products in solutions, dispersions or dusts,they may be used as agents for protecting plant and animal products suchas wool, fur, silk, wood and other cellulosic materials, regeneratedcellulose, cotton, leather, glue, paper, and plant latices from harmfulpests, especially molds (fungi), insects and bacteria While the materialto be protected is a raw ma- 3 terial or a finished product.

The solvents, dusts and aqueous suspensions generally used forconvenience of application of pesticides, have the common property ofpermitting projection of the materials through suitable jets or nozzlesonto the materials to be treated, and will be designated in the appendedclaims for convenience, as fluent carriers.

Since these addition products are not appreciably soluble in Water,leaching of the protective agent from fabrics that are treated withthese addition products and subjected to all weather conditions is not aserious problem.

The above description and examples are intended to be illustrative only.Any modification of or variation therefrom which conforms to the spiritof the invention is intended to be included within the scope of theclaims.

We claim:

1. A method of protecting materials which are capable of nourishingbacteria, fungi and insects from destruction by said pests whichcomprises bringing the material into contact with the addition productof an aliphatic substituted zinc dithoicarbamate and an amine having atleast one hydrogen atom in the amino group.

2. A method of protecting materials which are capable of nourishingbacteria, fungi and insects from destruction by said pests whichcomprises bringing the material into contact with the addition productof an alkyl substituted zinc dithiocarbamate and an amine having atleast one hydrogen atom in the amino group.

3. A method of protecting materials which are capable of nourishingbacteria, fungi and insects from destruction by said pests whichcomprises bringing the material into contact with the addition productof a dialkyl substituted zinc dithiocarbamate and an amine having atleast one hydrogen atom in the amino group.

4". A method of protecting materialscapabl'eof nourishing bacteria,fungi and insects from destruction by said'pests which comprisesbringing the material into contact with the addition product of zincdimethyl dithiocarbamate and an amine having at least one hydrogen atomin the amino group.

5. A method'of protecting materials which are capable of nourishingbacteria, fungi and insects from destruction by said pests whichcomprises bringing the material into contact with a mixture of a fluentcarrier and a small proportion of the addition product of zinc dimethyldithiocarbamate and ethylene diamine.

6. A method of protecting materials which are capable of nourishingbacteria, fungi and insects from destruction by said pests whichcomprises bringing the material into contact with a mixture of a fluentcarrier and a small proportion of the addition product of zinc dimethyldithiocarbamate and cyclohexyl amine.

7. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wetting agent and the active ingredient being theproduct of the chemical addition of the Zinc salt of an N-aliphaticsubstituted dithiocarbamic acid with an amine in which each amino groupcontains at least one hydrogen atom.

8. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wetting agent and the active ingredient being theproduct of the chemical addition of the zinc salt of an N-alkylsubstituted dithiocarbamic acid with an amine in which each amino groupcontains at least one hydrogen atom.

9. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wetting agent and the active in redient being theproduct of the chemical addition of the zinc salt of an N-dialkylsubstituted dithiocarbamic acid with an amine in which each amino groupcontains at least one hydrogen atom.

10. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wetting agent and the active ingredient being theproduct of the chemical addition of zinc dimethyl dithiocarbamate withan amine in which each amino group contains at least one hydrogen atom.

11. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wettng agent and the active ingredient being theproduct of the chemical addition of zinc dimethyl dithiocarbamate withethylene diamine.

12. A pesticidal composition essentially containing particles of anactive ingredient dispersed in a fluent carrier, the carrier being anaqueous solution of a wetting agent and the active ingredient being theproduct of the chemical addition of zinc dimethyl dithiocarbamate withcyclohexylamine.

13. A pesticidal composition comprising an active ingredient and afinely-divided solid carrier, the active ingredient being the product ofthe chemical addition of a zinc salt of an N-aliphatic substituteddithiocarbamic acid with an amine 7 having at least one hydrogen atom inthe amino group.

14. A composition according to claim 13 wherein the active ingredient isthe addition product of zinc dimethyl dithiocarbamate and cyclohexylamine.

WILLIAM D. STEWART. JOHN H. STANDEN.

REFERENCES CITED UNITED STATES PATENTS Name Date Tisdale et a1 Sept. 11,1934 Number Number Name Date 2,243,544 ter Horst May 27, 1941 2,317,765Hester Apr. 27, 1943 2,321,301 Lichty June 8, 1943 FOREIGN PATENTSNumber Country Date 8103/32 Australia Apr. 24. 1933 OTHER REFERENCESGuy: Investigation of Organic Compounds as Insecticides, Bull. N0. 206,Technical No. 19, February 1937, University of Delaware Agri. Exp.Station, pp. 54-55, 167-22.

1. A METHOD OF PROTECTING MATERIAL WHICH ARE CAPABLE OF NOURISHINGBACTERIA, FUNGI AND INSECTS FROM DESTRUCTION BY SAID PESTS WHICHCOMPRISES BRINGING THE MATERIAL INTO CONTACT WITH THE ADDITION PRODUCTOF AN ALIPHATIC SUBSTITUTED ZINC DITHOICARBOMATE AND AN AMINE HAVING ATLEAST ONE HYDROGEN ATOM IN THE AMINO GROUP.